High-toughness high-filling polypropylene material and preparation method thereof

Abstract

The invention discloses a high-toughness high-filling polypropylene material and a preparation method thereof. The composite material is prepared from the following components in parts by weight: 30-45 parts of polypropylene resin, 15-25 parts of a toughening agent, 0-5 parts of a compatilizer, 40 parts of filling minerals, 0.2-0.4 part of an antioxidant and 0.2-0.3 part of a nucleating agent, wherein the toughening agent is at least one of hydrogenated styrene-isobutylene-styrene, an ethylene-octylene copolymer and high-density polyethylene. According to the invention, hydrogenated styrene-isobutylene-styrene (SIBS) or ethylene-octylene copolymer (POE) is selected as the flexibilizer, and the addition proportion of the flexibilizer is controlled, so that the high-filling polypropylene material has good low-temperature high-speed impact toughness while having a lower linear expansion coefficient.

Description

Technical Field

[0001] The invention relates to the field of materials, in particular to a high-toughness and high-filling polypropylene material and a preparation method thereof. Background Art

[0002] Polypropylene resin has excellent impact toughness. In the field of automotive application materials, passenger cars and commercial vehicles are generally suitable for polypropylene talc-filled modified composite materials. Among them, highly filled (filling amount ≥ 30%) polypropylene materials are often suitable for products with higher precision requirements, such as all-plastic tailgates, which require a very low linear expansion coefficient to meet the gap between assembled parts in high and low temperature environments. However, in the case of high filling, the low-temperature toughness of polypropylene materials is significantly reduced, which is specifically manifested in a significant decrease in the type of damage in the low-temperature high-speed impact toughness test. Therefore, it is of certain practical significance to improve the low-temperature toughness modification of highly filled polypropylene materials. Summary of the invention

[0003] In view of this, the present invention provides a high-toughness and high-filled polypropylene material and a preparation method thereof to solve the problems raised in the above background technology. In the case of high filling of talc in polypropylene, the polypropylene has a low linear expansion coefficient (≤3.5x 10 -5 cm / cm / ℃) and good low temperature high impact toughness.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] In a first aspect, the present invention discloses a high-toughness and high-filled polypropylene material, which is prepared from the following components in parts by weight:

[0006]

[0007] The toughening agent is at least one of hydrogenated styrene-isobutylene-styrene, ethylene-octene copolymer, and high-density polyethylene.

[0008] As a further solution of the present invention: the compatibilizer is at least one of polypropylene grafted with maleic anhydride and ethylene methyl acrylate grafted with glycidyl methacrylate.

[0009] As a further solution of the present invention: the filler mineral is talcum powder, and the addition amount thereof is not less than 30w%.

[0010] As a further solution of the present invention: the melt index of the polypropylene resin is 80-100 g / 10 min.

[0011] As a further solution of the present invention: the antioxidant is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris(2,4-di-tert-butylphenyl) phosphite.

[0012] As a further solution of the present invention: the nucleating agent is an α-crystalline nucleating agent.

[0013] In a second aspect, the present invention discloses a method for preparing the high-toughness and high-filled polypropylene material as described above, comprising the following steps:

[0014] Weigh each component according to weight, mix the polypropylene resin, toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of the parallel twin-screw extruder, and feed the filling mineral into the side feeding port. After melting, extrusion and granulation, high-toughness and high-filling polypropylene material is obtained.

[0015] As a further scheme of the present invention: the temperature of zone 1 of the parallel twin-screw extruder is 200°C-230°C, the temperature of zone 2 is 210°C-240°C, the temperature of zone 3 is 215°C-245°C, the temperature of zone 4 is 215°C-245°C, the temperature of zone 5 is 215°C-245°C, the temperature of zone 6 is 220°C-250°C, the temperature of zone 7 is 220°C-250°C, the temperature of zone 8 is 220°C-250°C, the die head temperature is 225°C-255°C, the screw speed is 400rpm-600rpm, and the ratio L / D of screw length L to diameter D is 35-45.

[0016] As a further solution of the present invention: the parallel twin-screw extruder has four groups of ZME kneading blocks on the screw shearing end and one group of reverse kneading blocks on the homogenizing end; and / or the screw shape of the parallel twin-screw extruder is a single-thread.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. The present invention selects hydrogenated styrene-isobutylene-styrene (SIBS) or ethylene-octene copolymer (POE) as a toughening agent and controls the addition ratio of the toughening agent, so that the highly filled polypropylene material has a lower linear expansion coefficient and good low-temperature and high-speed impact toughness.

[0019] 2. The present invention selects ethylene methyl acrylate grafted glycidyl methacrylate (EBA-g-GMA) as a compatibilizer and controls the addition ratio of the compatibilizer, so that the high-filled polypropylene material has a lower linear expansion coefficient and the low-temperature and high-speed impact toughness is further improved.

[0020] 3. The preparation method of the present invention adopts a special screw assembly, the process is relatively simple, and the equipment used is common polymer processing equipment except for the special screw original parts, without additional cost increase, which is conducive to industrial production. The AME kneading block helps to increase the dispersion and distribution uniformity of mineral powder in PP resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a physical picture of the ZME kneading block in the present invention;

[0022] Figure 2 This is a physical picture of a common kneading block in the present invention; DETAILED DESCRIPTION

[0023] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0025] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0026] Polypropylene resin, with a molecular weight of 80 g / min, selected from SK Company;

[0027] SIBS toughening agent, brand D1170, selected from Kraton Corporation;

[0028] POE toughening agent, brand DF610, selected from Mitsui Chemicals;

[0029] Compatibilizer, ethylene methyl acrylate grafted glycidyl methacrylate (EBA-g-GMA): 4170, selected from DuPont.

[0030] Antioxidants: Antioxidant 1010 and Antioxidant 168 were mixed in a mass ratio of 2:1 and both were from BASF;

[0031] Nucleating agent, brand NA-11, selected from ADK Company;

[0032] All materials are commercially available common products.

[0033] It is to be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, so that the technical solution of the present invention is clearer, and it does not mean that the present invention can only use the above reagents, and the specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0034] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0035] Example 1

[0036] Weigh 37 parts of polypropylene resin, 20 parts of SIBS toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, and melt-extrude and granulate to obtain a high-toughness and high-filled polypropylene material.

[0037] The working parameters of the horizontal twin-screw extruder are: the temperature of zone 1 is 220℃, the temperature of zone 2 is 225℃, the temperature of zone 3 is 230℃, the temperature of zone 4 is 230℃, the temperature of zone 5 is 230℃, the temperature of zone 6 is 235℃, the temperature of zone 7 is 235℃, the temperature of zone 8 is 235℃, the die head temperature is 240℃, and the screw speed is 600rpm. The screw shape of the parallel twin-screw extruder is single-thread; the ratio of screw length L to diameter D L / D is 40; four groups of ZME kneading blocks are provided on the shear end of the screw, and a group of reverse kneading blocks are provided on the homogenizing end.

[0038] Example 2

[0039] Weigh 35 parts of polypropylene resin, 20 parts of SIBS toughening agent, 5 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, melt extrude and granulate, and obtain a high-toughness and high-filled polypropylene material.

[0040] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0041] Example 3

[0042] Weigh 40 parts of polypropylene resin, 20 parts of SIBS toughening agent, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent. After mixing the polypropylene resin, SIBS toughening agent, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, and melt extrude and granulate to obtain a high-toughness and high-filling polypropylene material.

[0043] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0044] Example 4

[0045] Weigh 37 parts of polypropylene resin, 20 parts of POE toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent, mix the polypropylene resin, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, and melt-extrude and granulate to obtain a high-toughness and high-filled polypropylene material.

[0046] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0047] Example 5

[0048] Weigh 35 parts of polypropylene resin, 20 parts of POE toughening agent, 5 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent, mix the polypropylene resin, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, and melt-extrude and granulate to obtain a high-toughness and high-filling polypropylene material.

[0049] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0050] Example 6

[0051] Weigh 40 parts of polypropylene resin, 20 parts of POE toughening agent, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent. After mixing the polypropylene resin, POE toughening agent, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, and melt extrude and granulate to obtain a high-toughness and high-filling polypropylene material.

[0052] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0053] Example 7

[0054] Weigh 37 parts of polypropylene resin, 5 parts of SIBS toughening agent, 15 parts of POE toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, melt extrude and granulate, and obtain a high-toughness and high-filled polypropylene material.

[0055] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0056] Example 8

[0057] Weigh 37 parts of polypropylene resin, 10 parts of SIBS toughening agent, 10 parts of POE toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, melt extrude and granulate, and obtain a high-toughness and high-filled polypropylene material.

[0058] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0059] Example 9

[0060] Weigh 37 parts of polypropylene resin, 15 parts of SIBS toughening agent, 5 parts of POE toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, melt extrude and granulate, and obtain a high-toughness and high-filled polypropylene material.

[0061] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0062] Comparative Example 1

[0063] Weigh 45 parts of polypropylene resin, 15 parts of SIBS toughening agent, 40 parts of filler mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent. After mixing the polypropylene resin, SIBS toughening agent, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filler mineral directly into the side feeding port, and melt-extrude and granulate to obtain a polypropylene material.

[0064] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0065] Comparative Example 2

[0066] Weigh 35 parts of polypropylene resin, 25 parts of SIBS toughening agent, 40 parts of filler mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent. After mixing the polypropylene resin, SIBS toughening agent, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filler mineral directly into the side feeding port, and melt-extrude and granulate to obtain a polypropylene material.

[0067] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0068] Comparative Example 3

[0069] Weigh 45 parts of polypropylene resin, 15 parts of POE toughening agent, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent, mix the polypropylene resin, POE toughening agent, nucleating agent and antioxidant, feed them to the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly to the side feeding port, melt extrude and granulate, and obtain a polypropylene material.

[0070] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0071] Comparative Example 4

[0072] Weigh 35 parts of polypropylene resin, 25 parts of POE toughening agent, 40 parts of filling mineral, 0.3 parts of antioxidant, and 0.3 parts of nucleating agent, mix the polypropylene resin, POE toughening agent, nucleating agent and antioxidant, feed them to the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly to the side feeding port, melt extrude and granulate, and obtain a polypropylene material.

[0073] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0074] Comparative Example 5

[0075] Weigh 60 parts of polypropylene resin, 40 parts of filler minerals, 0.3 parts of antioxidants, and 0.3 parts of nucleating agents. After mixing the polypropylene resin, nucleating agent, and antioxidant, feed them to the main feeding port of a horizontal twin-screw extruder, feed the filler minerals directly to the side feeding port, and melt-extrude and granulate to obtain a polypropylene material.

[0076] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0077] Comparative Example 6

[0078] Weigh 57 parts of polypropylene resin, 40 parts of filler minerals, 3 parts of compatibilizers, 0.3 parts of antioxidants, and 0.3 parts of nucleating agents. After mixing the polypropylene resin, nucleating agent, compatibilizer and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filler minerals directly into the side feeding port, and melt-extrude and granulate to obtain a polypropylene material.

[0079] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0080] Comparative Example 7

[0081] Weigh 55 parts of polypropylene resin, 40 parts of filler minerals, 5 parts of compatibilizers, 0.3 parts of antioxidants, and 0.3 parts of nucleating agents. After mixing the polypropylene resin, nucleating agent, compatibilizer, and antioxidant, feed them to the main feeding port of a horizontal twin-screw extruder, feed the filler minerals directly to the side feeding port, and melt-extrude and granulate to obtain a polypropylene material.

[0082] Wherein, the operating parameters of the horizontal twin-screw extruder are the same as those in Example 1.

[0083] Comparative Example 8

[0084] Weigh 37 parts of polypropylene resin, 10 parts of SIBS toughening agent, 10 parts of POE toughening agent, 3 parts of compatibilizer, 40 parts of filling mineral, 0.3 parts of antioxidant and 0.3 parts of nucleating agent, mix the polypropylene resin, SIBS toughening agent, POE toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of a horizontal twin-screw extruder, feed the filling mineral directly into the side feeding port, melt extrude and granulate, and obtain a high-toughness and high-filled polypropylene material.

[0085] The working parameters of the horizontal twin-screw extruder are: the temperature of zone 1 is 220℃, the temperature of zone 2 is 225℃, the temperature of zone 3 is 230℃, the temperature of zone 4 is 230℃, the temperature of zone 5 is 230℃, the temperature of zone 6 is 235℃, the temperature of zone 7 is 235℃, the temperature of zone 8 is 235℃, the die head temperature is 240℃, and the screw speed is 600rpm. The screw shape of the parallel twin-screw extruder is single-thread; the ratio of screw length L to diameter D L / D is 40; a common kneading block is provided on the shearing end of the screw, and a set of reverse kneading blocks is provided on the homogenizing end.

[0086] The polypropylene materials obtained in the examples and comparative examples were subjected to the following performance tests:

[0087] Linear expansion coefficient: tested according to ISO 11359-2 standard, temperature range is -30℃~100℃, test direction is longitudinal;

[0088] Low temperature impact performance: -30℃, tested according to ASTM standard, test speed is 2.2m / s. Test judgment classification: YD: deep drawing crack after yielding YS: stable crack extension after yielding YU: unstable crack extension after yielding NY: unyielding

[0089] The performance test results are shown in Table 1.

[0090] Table 1

[0091]

[0092] Embodiments 1 to 6 are a kind of high-toughness high-filled polypropylene material prepared by adjusting the proportion of compatibilizer EBA-GMA under fixed 20 parts of SIBS / POE toughening agent and 40 parts of talcum powder filling. It can be seen from Table 1 that the compounding between compatibilizers can significantly improve the low-temperature high-speed impact performance. When 3 / 5 parts are added, the impact failure type evolves from YU to YS. At the same time, the linear expansion coefficient of the high-filled polypropylene material is also improved. This is because the methyl acrylate group in EBA-GMA can well coat talcum powder, and the polar group of glycidyl methacrylate increases the polarity of talcum powder through the ring opening of epoxy group. At the same time, the vinyl group can be well compatible with polypropylene, thereby achieving the purpose of enhancing the dispersion and distribution of talcum powder in polypropylene. The toughening agent and the compatibilizer have a synergistic effect, enhancing the polarity of the high talcum powder filled polypropylene, so that the polar SIBS / POE toughening agent can be better dispersed in the high talcum powder filled polypropylene.

[0093] Examples 7 to 9 are high-toughness, high-filled polypropylene materials prepared by adjusting the ratio of toughening agent SIBS / POE under a fixed filling of 3 parts of EBA-GMA compatibilizer and 40 parts of talcum powder. As can be seen from Table 1, the compounding of toughening agents can significantly improve the low-temperature and high-speed impact performance. Example 8 achieves the best failure type of YD, and at the same time, the linear expansion coefficient of the filled polypropylene material remains the lowest.

[0094] Comparative Examples 1 to 4 are filled with 40 parts of talc powder and no EBA-GMA compatibilizer, compared with Examples 3 and 6. With the increase of toughening agent, the low-temperature high-speed impact failure type is NY when no toughening agent is added, YU when 15 / 20 parts of toughening agent are added, and YS when added to 25 parts, indicating that the increase of toughening agent can improve the failure type of low-temperature high-speed impact, but the addition ratio is large, that is, 25 parts to reach YS type.

[0095] Comparative Examples 5 to 7 are filled with 40 parts of talc powder and no toughening agent is added. As the compatibilizer is increased, the linear expansion coefficient decreases, but the low-temperature high-speed impact performance is not improved.

[0096] In summary, the present invention adopts a specific toughening agent, a compatibilizer and a special thread design, and controls the appropriate ratio between the toughening agents to prepare a high-toughness, high-filled polypropylene material, which has a low linear expansion coefficient (≤3.5x10-5cm / cm / ℃) and good low-temperature and high-speed impact performance.

[0097] Although this specification is described according to implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0098] Therefore, the above description is only a preferred embodiment of the present application and is not intended to limit the scope of implementation of the present application; that is, all equivalent changes made according to the scope of the claims of the present application are within the protection scope of the claims of the present application.

Claims

1. A high-toughness and high-filled polypropylene material, characterized in that: It is prepared from the following components in parts by weight: The toughening agent is at least one of hydrogenated styrene-isobutylene-styrene, ethylene-octene copolymer, and high-density polyethylene.

2. The high-toughness and high-filled polypropylene material according to claim 1, characterized in that: The compatibilizer is at least one of polypropylene grafted with maleic anhydride and ethylene methyl acrylate grafted with glycidyl methacrylate.

3. The high-toughness and high-filled polypropylene material according to claim 1, characterized in that: The filler mineral is talcum powder, and the addition amount thereof is not less than 30w%.

4. The high-toughness and high-filled polypropylene material according to claim 1, characterized in that: The melt index of the polypropylene resin is 80-100 g / 10 min.

5. The high-toughness and high-filled polypropylene material according to claim 1, characterized in that: The antioxidant is prepared by compounding pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris(2,4-di-tert-butylphenyl) phosphite.

6. The high-toughness and high-filled polypropylene material according to claim 1, characterized in that: The nucleating agent is an α-crystal nucleating agent.

7. The method for preparing the high-toughness and high-filling polypropylene material according to any one of claims 1 to 6, characterized in that: The following steps are involved: Weigh each component according to weight, mix the polypropylene resin, toughening agent, compatibilizer, nucleating agent and antioxidant, feed them into the main feeding port of the parallel twin-screw extruder, and feed the filling mineral into the side feeding port. After melting, extrusion and granulation, high-toughness and high-filling polypropylene material is obtained.

8. The preparation method according to claim 7, characterized in that: The temperature of zone 1 of the parallel twin-screw extruder is 200°C-230°C, the temperature of zone 2 is 210°C-240°C, the temperature of zone 3 is 215°C-245°C, the temperature of zone 4 is 215°C-245°C, the temperature of zone 5 is 215°C-245°C, the temperature of zone 6 is 220°C-250°C, the temperature of zone 7 is 220°C-250°C, the temperature of zone 8 is 220°C-250°C, the die head temperature is 225°C-255°C, the screw speed is 400rpm-600rpm, and the ratio L / D of screw length L to diameter D is 35-45.

9. The preparation method according to claim 7, characterized in that: The parallel twin-screw extruder has four groups of ZME kneading blocks on the screw shearing end and one group of reverse kneading blocks on the homogenizing end; and / or, the screw shape of the parallel twin-screw extruder is a single-thread.

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